CN108306019B - Preparation method of carbon-doped lithium iron phosphate - Google Patents
Preparation method of carbon-doped lithium iron phosphate Download PDFInfo
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- CN108306019B CN108306019B CN201810083392.0A CN201810083392A CN108306019B CN 108306019 B CN108306019 B CN 108306019B CN 201810083392 A CN201810083392 A CN 201810083392A CN 108306019 B CN108306019 B CN 108306019B
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- lithium hydroxide
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 150
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000012074 organic phase Substances 0.000 claims abstract description 33
- 238000003756 stirring Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000005416 organic matter Substances 0.000 claims abstract description 24
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 23
- 239000010452 phosphate Substances 0.000 claims abstract description 23
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012071 phase Substances 0.000 claims abstract description 20
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 239000010936 titanium Substances 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 6
- 238000004891 communication Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 238000009461 vacuum packaging Methods 0.000 claims description 6
- 238000005056 compaction Methods 0.000 abstract description 8
- 239000007789 gas Substances 0.000 abstract description 6
- 239000010865 sewage Substances 0.000 abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 8
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- 239000012467 final product Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910017709 Ni Co Inorganic materials 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000011164 primary particle Substances 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910000398 iron phosphate Inorganic materials 0.000 description 3
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- -1 ion phosphate Chemical class 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910003321 CoFe Inorganic materials 0.000 description 1
- 239000012692 Fe precursor Substances 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910012923 LiCoO2In Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013275 LiMPO Inorganic materials 0.000 description 1
- 229910001305 LiMPO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- WFGBXPXOFAFPTO-UHFFFAOYSA-N [P].[Fe].[Li] Chemical compound [P].[Fe].[Li] WFGBXPXOFAFPTO-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010450 olivine Substances 0.000 description 1
- 229910052609 olivine Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of carbon-doped lithium iron phosphate. Stirring and mixing dialkyl phosphate and a lithium hydroxide solution, standing to obtain a first organic phase and a first water phase, separating the first organic phase from the first water phase, introducing nitrogen into the first organic phase in a closed reaction kettle, mixing, adding ferrocene and butyl titanate, and uniformly mixing and stirring to obtain a mixed organic matter; and adding the mixed organic matter into a fluidized bed furnace in a spraying manner, simultaneously adding air, introducing sulfur dioxide gas, continuously reacting for 2-3 hours, introducing nitrogen for 30-60min, cooling and collecting the material to obtain the carbon-doped lithium iron phosphate. The method has the advantages of simple process and low cost, and the obtained carbon-doped lithium iron phosphate is uniformly doped in the lithium iron phosphate, so that the method has better conductivity, high compaction density and tap density, short flow, small sewage generation amount and low cost.
Description
Technical Field
The invention relates to a preparation method of carbon-doped lithium iron phosphate, belonging to the field of new energy materials of lithium batteries.
Background
Lithium iron phosphate (molecular formula: LiFePO)4(ii) a English: lithonium ion phosphate; also known as lithium iron phosphate, lithium iron phosphorus; LFP for short) is a positive electrode material of a lithium ion battery. AyMPO was first disclosed by NTT in Japan from 19964(A is an alkali metal, M is a combination of CoFe: LiFeCoPO4) After the olivine-structured lithium battery cathode material, research group of john.b. goodenough et al, texas state university, 1997, also reported LiFePO4Reversibly incorporate and remove lithium, and the olivine structure (LiMPO) is published in the United states in much the same way as in Japan4) This material has received great attention and has led to extensive research and rapid development. Compared with the conventional lithium ion secondary battery cathode material, the spinel-structured LiMn2O4And laminated LiCoO2In contrast, LiMPO4The raw materials have wider sources, lower price and no environmental pollution.
It has the following properties: high energy density: the theoretical specific capacity is 170mAh/g, and the actual specific capacity of the product can exceed 140mAh/g (0.2C,25 ℃); safety, is the safestLithium ion batteryA positive electrode material; does not contain any harmful substances to human bodyHeavy metal elements(ii) a The service life is long, and the charging and discharging can be carried out for more than 2000 times under the condition of 100 percent DOD; the lithium iron phosphate has good lattice stability, and the lithium ion is not greatly influenced by the insertion and the extraction of the lithium ion, so the lithium iron phosphate has good reversibilityGuide tube Electrical materialAnd doping to modify the electrode. )
Lithium iron phosphate batteryService life ofThe life is closely related to the use temperature, and the use temperature is too low or too high, so that great adverse potential hazards are generated in the charging and discharging processes and the use process. Especially, when the lithium iron phosphate battery is used on electric automobiles in northern China, the working environment temperature of the lithium iron phosphate battery can not be regulated to keep the performance of the lithium iron phosphate battery in autumn and winter, or the power supply is too low. The problem that the constant temperature working environment of the lithium iron phosphate battery needs to consider space limitation is solved domestically, and the more common solution is to useAerogel feltAsHeat insulation layer。
Charging performance
The lithium battery made of the lithium iron phosphate anode material can be charged with a large multiplying power, and the battery can be fully charged within 1 hour at the fastest speed.
Specific physical parameters:
apparent density: 0.7g/mL
Tap density: 1.2g/mL
The median diameter: 2-6um
Specific surface area<30m2/g
Smear parameters:
LiFePo4:C:PVDF＝90:3:7
pole piece compaction density: 2.1-2.4g/mL
Electrochemical performance:
gram capacity >155mAh/g test conditions: half cell, 0.2C, voltage 4.0-2.0V
Cycle number: 2000 times
The current conventional techniques are: firstly, preparing iron precursors such as iron phosphate, ferrous oxalate, ferric oxide and the like, and then doping a lithium source and a carbon source for high-temperature sintering. However, there are the following problems:
1. carbon has a coated structure, which leads to poor conductivity, and an increase in the carbon content leads to a low energy density.
2. The process flow is long, the sewage production amount is large and the cost is high.
3. The compacted density is low, generally not higher than 2.4g/mL, and the tap density is low, generally only 1.2 g/mL.
Disclosure of Invention
In view of the above, the invention provides a preparation method of carbon-doped lithium iron phosphate, which has the advantages of simple process and low cost, and the obtained carbon-doped lithium iron phosphate is uniformly doped in lithium iron phosphate, and has the advantages of better conductivity, high compaction density and tap density, short flow, small sewage generation amount and low cost.
The invention solves the technical problems by the following technical means:
a preparation method of carbon-doped lithium iron phosphate comprises the following steps:
(1) stirring and mixing dialkyl phosphate and a lithium hydroxide solution, standing to obtain a first organic phase and a first water phase, separating the first organic phase from the first water phase, introducing nitrogen into the first organic phase in a closed reaction kettle, mixing, adding ferrocene and butyl titanate, and uniformly mixing and stirring to obtain a mixed organic matter;
(2) and (2) adding the mixed organic matter obtained in the step (1) into a fluidized bed furnace in a spraying mode, adding air at the same time, keeping the temperature in the fluidized bed furnace at 900-950 ℃, keeping the adding time of the mixed organic matter at 4-5 hours, continuing to introduce air for reaction for 1-2 hours, stopping introducing air, introducing sulfur dioxide gas, continuing to react for 2-3 hours, then introducing nitrogen for 30-60min, cooling and collecting the material, thus obtaining the carbon-doped lithium iron phosphate.
The concentration of the lithium hydroxide solution in the step (1) is 1.5-2mol/L, the stirring speed in the reaction process of the dialkyl phosphate and the lithium hydroxide solution is 150-250r/min, the mixing reaction time is 15-20min, the mixing reaction temperature is 55-60 ℃, and the standing time is 15-20 min.
The preparation method of the lithium hydroxide solution in the step (1) is to dissolve battery-grade lithium hydroxide into deionized water to prepare the solution, and the separated first water phase is returned to prepare the lithium hydroxide solution.
In the step (1), the molar ratio of dialkyl phosphate to lithium hydroxide in the lithium hydroxide solution is 1:1, and the molar ratio of lithium in the first organic phase to titanium in iron and butyl titanate in ferrocene is 1: 0.0075-0.008, the mixing time of the first organic phase and the ferrocene and butyl titanate is 30-60min, the stirring speed is 150-.
In the step (2), the total volume of the added mixed organic matters is 1/10-1/5 of the volume of the boiling furnace, the volume of the added air is 3000-5000 times of the volume of the mixed organic matters, the particle size of spray droplets is maintained to be 1-5 microns when the mixed organic matters are added in a spraying manner, the height-diameter ratio of the boiling furnace is more than 3, and the mole number of the added sulfur dioxide is 20-50 times of the mole number of iron in the added mixed organic matters.
The fluidized bed furnace is communicated with the induced draft fan, a titanium screen is arranged at the communication position of the fluidized bed furnace and the induced draft fan, the mesh number of the titanium screen is 1200-1500 meshes, an outlet of the induced draft fan is absorbed by the spray tower, and the absorption liquid is alkali liquor.
The volume of the introduced nitrogen is 2 to 5 times of the volume of the sulfur dioxide.
And (4) continuously rotating the induced draft fan in the cooling process, and taking out the materials for screening, deironing and vacuum packaging when the induced draft fan is cooled to the temperature of 130-160 ℃.
The invention reacts dialkyl phosphate with lithium hydroxide to obtain dialkyl lithium phosphate, then mixes ferrocene and butyl titanate, generates combustion reaction under the condition of high temperature and air existence, alkyl in the dialkyl lithium phosphate, phenyl in the ferrocene and butyl alcohol in the butyl titanate are combusted into carbon dioxide and water, then is pumped away by a draught fan, controls the adding amount of air, thereby controlling the degree of carbon combustion in the lithium phosphate, and leads the lithium, iron and phosphate radical to react to obtain lithium iron phosphate, and leads the lithium iron phosphate to be doped with titanium due to the mixing of the butyl titanate, thereby improving the compaction of the product, simultaneously, as the air addition can generate ferric iron, sulfur dioxide is added in the later period, the ferric iron in the lithium iron phosphate is reduced into ferrous iron, the ferric iron content of the final product is lower than 10ppm, meanwhile, due to the weak reducibility of the sulfur dioxide, iron ions are prevented from being reduced into iron simple substances, and magnetic foreign matters can be effectively reduced.
Meanwhile, unreacted sulfur dioxide and sulfur trioxide obtained by the reaction are absorbed by alkali liquor.
The final product test results were as follows:
| index (I) | Iron content | Phosphorus content | D10 | D50 | D90 |
| Numerical value | 35-35.2％ | 19.4-19.5％ | 30-40nm | 80-95nm | 150-250nm |
| D100 | Ca | Mg | Na | Ni | Co |
| ＜400nm | ＜10ppm | ＜10ppm | ＜10ppm | ＜10ppm | ＜10ppm |
| Mn | Zn | Cu | Ti | Al | Si |
| ＜15ppm | ＜10ppm | ＜5ppm | 0.15-0.25％ | ＜10ppm | ＜10ppm |
| Tap density | Sulfur | Chloride ion | BET | Primary particle diameter | Carbon content |
| 1.35-1.5g/mL | ＜5ppm | 2-3ppm | 5-15m2/g | 10-15nm | 0.5-1％ |
| Magnetic foreign matter | Ferric iron | Density of compaction | |||
| ＜10ppb | ＜10ppm | ＞2.65g/mL |
The method does not adopt a precursor synthesis process, has short flow, can obtain the lithium iron phosphate by one-step synthesis, is doped with titanium and carbon, generates 4-5 tons of wastewater for one ton of products in the wastewater amount generated in the preparation process, generates nearly 100 tons of wastewater containing ammonia nitrogen and phosphate radical for one ton of products in the conventional process by only preparing the precursor, greatly reduces the cost for preparing the lithium iron phosphate by a one-step method, and has the cost of about 60 percent for the process for preparing the lithium iron phosphate by adopting the iron phosphate as the precursor at present.
The invention has the beneficial effects that:
1. the process is simple, and each ton of products generates about 5 tons of wastewater, which is 1/20 of the conventional process.
2. The lithium iron phosphate doped with carbon and titanium is obtained by a one-step method, the process of synthesizing ferric salt precursor is not needed, the production efficiency is high, and the cost is low.
3. The obtained nano lithium iron phosphate has good dispersibility, low magnetic foreign matter and high tap density and compacted density.
Detailed Description
The present invention will be described in detail with reference to specific examples, in which the preparation method of carbon-doped lithium iron phosphate of this example includes the following steps:
(1) stirring and mixing dialkyl phosphate and a lithium hydroxide solution, standing to obtain a first organic phase and a first water phase, separating the first organic phase from the first water phase, introducing nitrogen into the first organic phase in a closed reaction kettle, mixing, adding ferrocene and butyl titanate, and uniformly mixing and stirring to obtain a mixed organic matter;
(2) and (2) adding the mixed organic matter obtained in the step (1) into a fluidized bed furnace in a spraying mode, adding air at the same time, keeping the temperature in the fluidized bed furnace at 900-950 ℃, keeping the adding time of the mixed organic matter at 4-5 hours, continuing to introduce air for reaction for 1-2 hours, stopping introducing air, introducing sulfur dioxide gas, continuing to react for 2-3 hours, then introducing nitrogen for 30-60min, cooling and collecting the material, thus obtaining the carbon-doped lithium iron phosphate.
The concentration of the lithium hydroxide solution in the step (1) is 1.5-2mol/L, the stirring speed in the reaction process of the dialkyl phosphate and the lithium hydroxide solution is 150-250r/min, the mixing reaction time is 15-20min, the mixing reaction temperature is 55-60 ℃, and the standing time is 15-20 min.
The preparation method of the lithium hydroxide solution in the step (1) is to dissolve battery-grade lithium hydroxide into deionized water to prepare the solution, and the separated first water phase is returned to prepare the lithium hydroxide solution.
In the step (1), the molar ratio of dialkyl phosphate to lithium hydroxide in the lithium hydroxide solution is 1:1, and the molar ratio of lithium in the first organic phase to titanium in iron and butyl titanate in ferrocene is 1: 0.0075-0.008, the mixing time of the first organic phase and the ferrocene and butyl titanate is 30-60min, the stirring speed is 150-.
In the step (2), the total volume of the added mixed organic matters is 1/10-1/5 of the volume of the boiling furnace, the volume of the added air is 3000-5000 times of the volume of the mixed organic matters, the particle size of spray droplets is maintained to be 1-5 microns when the mixed organic matters are added in a spraying manner, the height-diameter ratio of the boiling furnace is more than 3, and the mole number of the added sulfur dioxide is 20-50 times of the mole number of iron in the added mixed organic matters.
The fluidized bed furnace is communicated with the induced draft fan, a titanium screen is arranged at the communication position of the fluidized bed furnace and the induced draft fan, the mesh number of the titanium screen is 1200-1500 meshes, an outlet of the induced draft fan is absorbed by the spray tower, and the absorption liquid is alkali liquor.
The volume of the introduced nitrogen is 2 to 5 times of the volume of the sulfur dioxide.
And (4) continuously rotating the induced draft fan in the cooling process, and taking out the materials for screening, deironing and vacuum packaging when the induced draft fan is cooled to the temperature of 130-160 ℃.
Example 1
A preparation method of carbon-doped lithium iron phosphate comprises the following steps:
(1) stirring and mixing dialkyl phosphate and a lithium hydroxide solution, standing to obtain a first organic phase and a first water phase, separating the first organic phase from the first water phase, introducing nitrogen into the first organic phase in a closed reaction kettle, mixing, adding ferrocene and butyl titanate, and uniformly mixing and stirring to obtain a mixed organic matter;
(2) and (2) adding the mixed organic matter obtained in the step (1) into a fluidized bed furnace in a spraying mode, adding air at the same time, keeping the temperature in the fluidized bed furnace at 925 ℃, keeping the adding time of the mixed organic matter at 4.5 hours, continuing to introduce air for reacting for 1.5 hours, stopping introducing air, introducing sulfur dioxide gas, continuing to react for 2.5 hours, then introducing nitrogen for 45min, cooling and collecting the material, thus obtaining the carbon-doped lithium iron phosphate.
The concentration of the lithium hydroxide solution in the step (1) is 1.8mol/L, the stirring speed in the reaction process of the dialkyl phosphate and the lithium hydroxide solution is 195r/min, the mixing reaction time is 18min, the mixing reaction temperature is 58 ℃, and the standing time is 18 min.
The preparation method of the lithium hydroxide solution in the step (1) is to dissolve battery-grade lithium hydroxide into deionized water to prepare the solution, and the separated first water phase is returned to prepare the lithium hydroxide solution.
In the step (1), the molar ratio of dialkyl phosphate to lithium hydroxide in the lithium hydroxide solution is 1:1, and the molar ratio of lithium in the first organic phase to titanium in iron and butyl titanate in ferrocene is 1: 0.0076, mixing the first organic phase with the ferrocene and the butyl titanate for 45min, stirring at 185r/min, and stirring at room temperature.
In the step (2), the total volume of the added mixed organic matters is 1/8 times of the volume of the fluidized bed furnace, the volume of the added air is 3500 times of the volume of the mixed organic matters, the particle size of spray droplets is maintained to be 2.5 micrometers when the mixed organic matters are added in a spraying manner, the height-diameter ratio of the fluidized bed furnace is more than 3, and the mole number of the added sulfur dioxide is 40 times of the mole number of iron in the added mixed organic matters.
The fluidized bed furnace is communicated with the induced draft fan, a titanium screen is arranged at the communication position of the fluidized bed furnace and the induced draft fan, the mesh number of the titanium screen is 1450 meshes, an outlet of the induced draft fan is absorbed by the spray tower, and the absorption liquid is alkali liquor.
The volume of nitrogen gas introduced was 4.5 times the volume of sulfur dioxide.
And (3) continuously rotating the induced draft fan in the cooling process, and taking out the materials for screening, deironing and vacuum packaging when the induced draft fan is cooled to the temperature of 150 ℃.
The final product test results were as follows:
| index (I) | Iron content | Phosphorus content | D10 | D50 | D90 |
| Numerical value | 35.12％ | 19.43％ | 35nm | 89nm | 193nm |
| D100 | Ca | Mg | Na | Ni | Co |
| 320nm | 4ppm | 6ppm | 7.1ppm | 4.5ppm | 1.2ppm |
| Mn | Zn | Cu | Ti | Al | Si |
| 5.5ppm | 6.2ppm | 3.5ppm | 0.165％ | 2.8ppm | 4.8ppm |
| Tap density | Sulfur | Chloride ion | BET | Primary particle diameter | Carbon content |
| 1.39g/mL | 4.3ppm | 2.7ppm | 12.5m2/g | 11nm | 0.95％ |
| Magnetic foreign matter | Ferric iron | Density of compaction | |||
| 3.5ppb | 7.8ppm | 2.68g/mL |
Example 2
A preparation method of carbon-doped lithium iron phosphate comprises the following steps:
(1) stirring and mixing dialkyl phosphate and a lithium hydroxide solution, standing to obtain a first organic phase and a first water phase, separating the first organic phase from the first water phase, introducing nitrogen into the first organic phase in a closed reaction kettle, mixing, adding ferrocene and butyl titanate, and uniformly mixing and stirring to obtain a mixed organic matter;
(2) and (2) adding the mixed organic matter obtained in the step (1) into a fluidized bed furnace in a spraying mode, adding air at the same time, keeping the temperature in the fluidized bed furnace at 925 ℃, keeping the adding time of the mixed organic matter at 4.3 hours, continuing to introduce air for reacting for 1.8 hours, stopping introducing air, introducing sulfur dioxide gas, continuing to react for 2.7 hours, then introducing nitrogen for 45min, cooling and collecting the material, thus obtaining the carbon-doped lithium iron phosphate.
The concentration of the lithium hydroxide solution in the step (1) is 1.9mol/L, the stirring speed in the reaction process of the dialkyl phosphate and the lithium hydroxide solution is 225r/min, the mixing reaction time is 18.5min, the mixing reaction temperature is 58.5 ℃, and the standing time is 18.9 min.
The preparation method of the lithium hydroxide solution in the step (1) is to dissolve battery-grade lithium hydroxide into deionized water to prepare the solution, and the separated first water phase is returned to prepare the lithium hydroxide solution.
In the step (1), the molar ratio of dialkyl phosphate to lithium hydroxide in the lithium hydroxide solution is 1:1, and the molar ratio of lithium in the first organic phase to titanium in iron and butyl titanate in ferrocene is 1: 0.0078, mixing the first organic phase with the ferrocene and the butyl titanate for 50min, stirring at the speed of 195r/min, and stirring at room temperature.
In the step (2), the total volume of the added mixed organic matter is 1/7 of the volume of the boiling furnace, the volume of the added air is 4000 times of the volume of the mixed organic matter, the particle size of spray droplets is maintained to be 2.5 micrometers when the mixed organic matter is added in a spraying manner, the height-diameter ratio of the boiling furnace is more than 3, and the mole number of the added sulfur dioxide is 42 times of the mole number of iron in the added mixed organic matter.
The fluidized bed furnace is communicated with the draught fan, a titanium screen is arranged at the communication position of the fluidized bed furnace and the draught fan, the mesh number of the titanium screen is 1350 meshes, an outlet of the draught fan is absorbed by the spray tower, and the absorption liquid is alkali liquor.
The volume of nitrogen gas introduced was 4.2 times the volume of sulfur dioxide.
And (4) continuously rotating the induced draft fan in the cooling process, and taking out the materials for screening, deironing and vacuum packaging when the induced draft fan is cooled to the temperature of 145 ℃.
The final product test results were as follows:
| index (I) | Iron content | Phosphorus content | D10 | D50 | D90 |
| Numerical value | 35.18％ | 19.47％ | 33nm | 89.2nm | 210.5nm |
| D100 | Ca | Mg | Na | Ni | Co |
| 330.5nm | 3ppm | 6.1ppm | 5.7ppm | 1.8ppm | 5.6ppm |
| Mn | Zn | Cu | Ti | Al | Si |
| 12.1ppm | 8.1ppm | 1.2ppm | 0.20％ | 6.2ppm | 1.5ppm |
| Tap density | Sulfur | Chloride ion | BET | Primary particle diameter | Carbon content |
| 1.39g/mL | 2.5ppm | 2.7ppm | 8.8m2/g | 13nm | 0.76％ |
| Magnetic foreign matter | Ferric iron | Density of compaction | |||
| 5.8ppb | 4.8ppm | 2.69g/mL |
Example 3
A preparation method of carbon-doped lithium iron phosphate comprises the following steps:
(1) stirring and mixing dialkyl phosphate and a lithium hydroxide solution, standing to obtain a first organic phase and a first water phase, separating the first organic phase from the first water phase, introducing nitrogen into the first organic phase in a closed reaction kettle, mixing, adding ferrocene and butyl titanate, and uniformly mixing and stirring to obtain a mixed organic matter;
(2) and (2) adding the mixed organic matter obtained in the step (1) into a fluidized bed furnace in a spraying mode, adding air at the same time, keeping the temperature in the fluidized bed furnace at 925 ℃, keeping the adding time of the mixed organic matter at 4.8 hours, continuing to introduce air for reacting for 1.7 hours, stopping introducing air, introducing sulfur dioxide gas, continuing to react for 2.8 hours, then introducing nitrogen for 45min, cooling and collecting the material, thus obtaining the carbon-doped lithium iron phosphate.
The concentration of the lithium hydroxide solution in the step (1) is 1.87mol/L, the stirring speed in the reaction process of the dialkyl phosphate and the lithium hydroxide solution is 198r/min, the mixing reaction time is 17min, the mixing reaction temperature is 58 ℃, and the standing time is 19 min.
The preparation method of the lithium hydroxide solution in the step (1) is to dissolve battery-grade lithium hydroxide into deionized water to prepare the solution, and the separated first water phase is returned to prepare the lithium hydroxide solution.
In the step (1), the molar ratio of dialkyl phosphate to lithium hydroxide in the lithium hydroxide solution is 1:1, and the molar ratio of lithium in the first organic phase to titanium in iron and butyl titanate in ferrocene is 1: 0.0079, mixing the first organic phase with the ferrocene and the butyl titanate for 58min, stirring at the speed of 195r/min, and mixing and stirring at room temperature.
In the step (2), the total volume of the added mixed organic matters is 1/9 of the volume of the fluidized bed furnace, the volume of the added air is 4800 times of the volume of the mixed organic matters, the particle size of spray droplets is maintained to be 4.2 micrometers when the mixed organic matters are added in a spraying manner, the height-diameter ratio of the fluidized bed furnace is more than 3, and the mole number of the added sulfur dioxide is 41 times of the mole number of iron in the added mixed organic matters.
The fluidized bed furnace is communicated with the induced draft fan, a titanium screen is arranged at the communication position of the fluidized bed furnace and the induced draft fan, the mesh number of the titanium screen is 1450 meshes, an outlet of the induced draft fan is absorbed by the spray tower, and the absorption liquid is alkali liquor.
The volume of nitrogen gas introduced was 4.1 times the volume of sulfur dioxide.
And (3) continuously rotating the induced draft fan in the cooling process, and taking out the materials for screening, deironing and vacuum packaging when the induced draft fan is cooled to the temperature of 150 ℃.
The final product test results were as follows:
| index (I) | Iron content | Phosphorus content | D10 | D50 | D90 |
| Numerical value | 35.12％ | 19.41％ | 38nm | 92.5nm | 215.8nm |
| D100 | Ca | Mg | Na | Ni | Co |
| 335.8nm | 5ppm | 4.2ppm | 3.5ppm | 4.2ppm | 1.8ppm |
| Mn | Zn | Cu | Ti | Al | Si |
| 10.8ppm | 8.1ppm | 2.5ppm | 0.23％ | 2.5ppm | 4.5ppm |
| Tap density | Sulfur | Chloride ion | BET | Primary particle diameter | Carbon content |
| 1.42g/mL | 2.5ppm | 2.5ppm | 12.5m2/g | 12.5nm | 0.57％ |
| Magnetic foreign matter | Ferric iron | Density of compaction | |||
| 2.5ppb | 2.5ppm | 2.72g/mL |
Comparing examples 1, 2, and 3 with the conventional process, i.e., the process of preparing iron phosphate, doping a carbon source, a lithium salt, and a titanium salt, mixing them, and calcining them, the results are as follows:
| ton product cost | Ton of product wastewater production | Power consumption per ton of product | |
| Example 1 | 4.42 ten thousand | 5.2 ton | 4000 kilowatt-hour |
| Example 2 | 4.5 ten thousand | 5.1 ton of | 4300 kilowatt hour |
| Example 3 | 4.62 million | 5.3 ton | 4200 kilowatt-hour |
| Conventional process | 7.2-7.5 ten thousand yuan | 100-110 ton | 10000 + 11000 kilowatt-hour |
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (7)
1. A preparation method of carbon-doped lithium iron phosphate is characterized by comprising the following steps:
(1) stirring and mixing dialkyl phosphate and a lithium hydroxide solution, standing to obtain a first organic phase and a first water phase, separating the first organic phase from the first water phase, introducing nitrogen into the first organic phase in a closed reaction kettle, mixing, adding ferrocene and butyl titanate, and uniformly mixing and stirring to obtain a mixed organic matter;
(2) adding the mixed organic matter obtained in the step (1) into a boiling furnace in a spraying manner, simultaneously adding air, keeping the temperature in the boiling furnace at 900-, the mole number of the added sulfur dioxide is 20-50 times of the mole number of the iron in the added mixed organic matter.
2. The method for preparing carbon-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: the concentration of the lithium hydroxide solution in the step (1) is 1.5-2mol/L, the stirring speed in the reaction process of the dialkyl phosphate and the lithium hydroxide solution is 150-250r/min, the mixing reaction time is 15-20min, the mixing reaction temperature is 55-60 ℃, and the standing time is 15-20 min.
3. The method for preparing carbon-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: the preparation method of the lithium hydroxide solution in the step (1) is to dissolve battery-grade lithium hydroxide into deionized water to prepare the solution, and the separated first water phase is returned to prepare the lithium hydroxide solution.
4. The method for preparing carbon-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: in the step (1), the molar ratio of dialkyl phosphate to lithium hydroxide in the lithium hydroxide solution is 1:1, and the molar ratio of lithium in the first organic phase to titanium in iron and butyl titanate in ferrocene is 1: 0.0075-0.008, the mixing time of the first organic phase and the ferrocene and butyl titanate is 30-60min, the stirring speed is 150-.
5. The method for preparing carbon-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: the fluidized bed furnace is communicated with the induced draft fan, a titanium screen is arranged at the communication position of the fluidized bed furnace and the induced draft fan, the mesh number of the titanium screen is 1200-1500 meshes, an outlet of the induced draft fan is absorbed by the spray tower, and the absorption liquid is alkali liquor.
6. The method for preparing carbon-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: the volume of the introduced nitrogen is 2 to 5 times of the volume of the sulfur dioxide.
7. The method for preparing carbon-doped lithium iron phosphate according to claim 1, wherein the method comprises the following steps: and (4) continuously rotating the induced draft fan in the cooling process, and taking out the materials for screening, deironing and vacuum packaging when the induced draft fan is cooled to the temperature of 130-160 ℃.
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